CN104045341A - Lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material and preparation method thereof - Google Patents
Lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material and preparation method thereof Download PDFInfo
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- CN104045341A CN104045341A CN201410288995.6A CN201410288995A CN104045341A CN 104045341 A CN104045341 A CN 104045341A CN 201410288995 A CN201410288995 A CN 201410288995A CN 104045341 A CN104045341 A CN 104045341A
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Abstract
The invention discloses a lead-free high-dielectric-constant multilayer ceramic capacitor dielectric material which uses BaTiO3 powder as a base material and is also composed of 0.6-1.2 wt% of (NiO)[1-x](NbO2.5)x (x=0.6-0.8), 0.2-0.5 wt% of (MnO)[1-y](NbO2.5)y (y=0.4-0.6) and 3.0-4.0 wt% of CaZrO3. The preparation method comprises the following steps: synthesizing the (NiO)1-x(NbO2.5)x compound, synthesizing the (MnO)1-y(NbO2.5)y compound, and synthesizing the CaZrO3; and proportioning, granulating, forming, discharging the adhesive, and sintering at 1250 DEG C. The calcium zirconate and the like are added to effectively improve the microstructure of the ceramic; all the ceramic components are environment-friendly; the traditional solid-phase process is beneficial to industrial production; the dielectric material has excellent dielectric properties; and within the temperature range of -55-150 DEG C, the capacitance change rate is within +/-15%, and the dielectric material has higher room-temperature dielectric constant (-4500).
Description
Technical field
The invention belongs to a kind of ceramic composition taking composition as feature, be specifically related to a kind of unleaded, high-k and there is X8R type medium material for multilayer ceramic capacitors of excellent temperature stability and preparation method thereof
Background technology
Along with chip multilayer ceramic capacitor (Multilayer Ceramic Capacitor, be called for short MLCC) fast development, for the requirement such as meet miniaturization, large capacity, apply in hot environment, ceramic medium material not only will possess high dielectric properties, and requires its rate of temperature change in wide temperature range, to present smooth variation characteristic.X8R (55 DEG C～150 DEG C, Δ C/C
25 DEG C≤ ± 15%) type MLCC is widely used in the industries such as Military Electronic Equipment and petroleum prospecting such as aerospace, tank electronics, military mobile communication, the control of weapon bullet and military signal monitoring with dielectric material.Barium titanate (BaTiO
3) base temperature-stable MLCC uses dielectric material because of its environmental sound, is the focus of research always.
But, the X8R dielectric material of present stage research, its room temperature dielectric constant is (lower than 3000) less than normal generally, growth requirement or the room temperature dielectric constant that can not meet miniaturization are high, but complicated process of preparation, be unfavorable for industrialization produce or synthesize in component leaded, harm environment.Along with the enhancing of people's Environmental awareness, the use of heavy metal is restricted, the development of restriction MLCC miniaturization.Therefore the dielectric material of, preparing a kind of unleaded high-k that is easy to suitability for industrialized production becomes particularly important.
Summary of the invention
Object of the present invention, though be that the Capacitance Shift Rate of the ceramic capacitor dielectric that overcomes prior art can reach the requirement of X8R, its specific inductivity is on the low side, even in component, contain heavy metal Pb, environmentally hazardous shortcoming.A kind of unleaded, high-k is provided and is beneficial to X8R type medium material for multilayer ceramic capacitors of suitability for industrialized production and preparation method thereof.
The present invention is achieved by following technical solution.
A kind of unleaded high-k medium material for multilayer ceramic capacitors, with BaTiO
3powder is base-material, on this basis, and (NiO) that additional mass percent is 0.6～1.2%
1-x(NbO
2.5)
x, wherein x=0.6～0.8; 0.2～0.5% (MnO)
1-y(NbO
2.5)
y, wherein y=0.4～0.6 and 3.0～4.0% CaZrO
3;
Described (NiO)
1-x(NbO
2.5)
xcompound is by NiO and Nb
2o
51-x:x/2 in molar ratio, wherein x=0.6～0.8 is synthetic;
Described (MnO)
1-y(NbO
2.5)
ycompound is by MnCO
3, Nb
2o
51-y:y/2 in molar ratio, wherein y=0.4～0.6 is synthetic;
Described CaZrO
3by CaCO
3and ZrO
21: 1 in molar ratio synthetic;
The preparation method of this unleaded high-k medium material for multilayer ceramic capacitors, has following steps:
(1) synthetic (NiO)
1-x(NbO
2.5)
xcompound, wherein x=0.6～0.8
By NiO, Nb
2o
51-x:x/2 in molar ratio, wherein x=0.6～0.8 batching, ball milling 4 hours after raw material mixes with deionized water, in 120 DEG C of oven dry, mistake 40 order sub-sieves, in 1000 DEG C of calcinings, is incubated 2 hours; Secondary ball milling 6 hours again, dries, crosses 80 order sub-sieves, makes (NiO)
1-x(NbO
2.5)
xcompound, wherein x=0.6～0.8;
(2) synthetic (MnO)
1-y(NbO
2.5)
ycompound, wherein y=0.4～0.6
By MnCO
3, Nb
2o
51-y:y/2 in molar ratio, wherein y=0.4～0.6 batching, ball milling 4 hours after raw material mixes with deionized water, in 120 DEG C of oven dry, mistake 40 order sub-sieves, in 800～1000 DEG C of calcinings; Secondary ball milling 6 hours again, dries, crosses 80 order sub-sieves, makes (MnO)
1-y(NbO
2.5)
ycompound, wherein y=0.4～0.6;
(3) synthetic CaZrO
3
By CaCO
3, ZrO
21:1 batching in molar ratio, ball milling 4 hours after raw material mixes with deionized water, in 120 DEG C of oven dry, mistake 40 order sub-sieves, in 1000 DEG C of calcinings, is incubated 2 hours, makes CaZrO
3;
(4) with BaTiO
3as base-material, the composition of additional following mass percent: 0.6～1.2% (NiO)
1-x(NbO
2.5)
x, wherein x=0.6～0.8; 0.2～0.5% (MnO)
1-y(NbO
2.5)
y, wherein y=0.4～0.6 and 3.0～4.0% CaZrO
3, institute joins raw material and mixes rear ball milling with deionized water 4～8 hours; The binding agent that after drying, additional mass percent is 7%, crosses 80 order sub-sieve granulations;
(5) the granulation powder of step (4) is pressed into green compact, after binder removal, in 1250 DEG C of sintering, is incubated 3 hours, make unleaded high-k medium material for multilayer ceramic capacitors.
The CaZrO of described step (4)
3the mass percent of addition is 3.5%.
The green compact of described step (5) are the disk green compact of Ф 15 × 1～1.3mm.
The green compact of described step (5) were warming up to 550 DEG C of binder removals through 3.5 hours, then rose to 1250 DEG C of sintering through 1 hour, were incubated 3 hours.
Beneficial effect of the present invention is as follows:
(1) medium material for multilayer ceramic capacitors of the present invention, by the interpolation of calcium zirconate etc., can effectively improve ceramic microtexture, promotes dielectric properties, the equal environmental friendliness of ceramic composition, and material be prepared as conventional solid-state method, be beneficial to suitability for industrialized production.
(2) medium material for multilayer ceramic capacitors of the present invention has good dielectric properties: in-55 DEG C～150 DEG C warm areas, rate of change of capacitance, in ± 15%, and has higher room temperature dielectric constant (～4500).
Embodiment
Below with reference to specific embodiment, the present invention is described in further detail:
Embodiment 1
First, use 2.2410g NiO and the 9.3033g Nb of electronic balance weighing analytical pure level (>=99%)
2o
5, mix, using deionized water as ball-milling medium, 4 hours post-dryings of ball milling, sieve, obtain (NiO) in 1000 DEG C of calcinings
0.3(NbO
2.5)
0.7compound, then secondary ball milling 6 hours, cross 80 order sub-sieves for subsequent use;
Use again the 5.7474g MnCO of electronic balance weighing analytical pure level (>=99%)
3with 6.6452g Nb
2o
5, mix, using deionized water as ball-milling medium, 4 hours post-dryings of ball milling, sieve, obtain (MnO) in 900 DEG C of calcinings
0.5(NbO
2.5)
0.5compound, then secondary ball milling 6 hours, cross 80 order sub-sieves for subsequent use;
Again by 22.3291g CaCO
3with 27.5114g ZrO
2mix, using deionized water as ball-milling medium, 4 hours post-dryings of ball milling, sieve, obtain CaZrO in 1000 DEG C of calcinings
3.
By 50g BaTiO
3, 0.45g (NiO)
0.3(NbO
2.5)
0.7, 0.1g (MnO)
0.5(NbO
2.5)
0.5with 1.75g CaZrO
3ball milling 4 hours after mixing with deionized water, the paraffin that after drying, additional mass percent is 7%, crosses 80 order sub-sieve granulations.
Moulding and sintering:
(1) powder after granulation is pressed under 3MPa to the disk green compact of Ф 15 × 1.2mm, be warming up to 550 DEG C of binder removals through 3.5 hours, rise to again 1250 DEG C of sintering through 1 hour, be incubated 5 hours, make unleaded high-k medium material for multilayer ceramic capacitors.
Evenly apply silver slurry in the upper and lower surface of resulting product, prepare electrode through 850 DEG C of burning infiltrations, make testing sample, test dielectric properties and TC characteristic.
The concrete proportioning raw materials of embodiment of the present invention 1-5 refers to table 1.
Table 1
Embodiment 1-5 refers to table 2 in the dielectric properties of the dielectric material of different annealing temperature and annealing time, and other manufacture craft of each embodiment is complete identical with embodiment 1.
Testing method of the present invention and test set are as follows:
(1) dielectric properties tests (AC test signals: frequency is 1kHz, voltage is 1V)
Use electrical capacity C and the loss tan δ of HEWLETT PACKARD4278A type capacitance tester test sample, and calculate the specific inductivity of sample, calculation formula is:
(2) TC characteristic test
Utilize the high low temperature circulation warm of GZ-ESPEC MPC-710P type case, HM27002 type electrical condenser C-T/V characteristic dedicated tester and HEWLETT PACKARD4278A to test.The electrical capacity of measure sample in warm area-55 DEG C～150 DEG C, adopts following formula to calculate rate of change of capacitance:
Table 2
The present invention is not limited to above-described embodiment, and the variation of a lot of details is possible, but therefore this do not run counter to scope and spirit of the present invention.
Claims (4)
1. a unleaded high-k medium material for multilayer ceramic capacitors, with BaTiO
3powder is base-material, on this basis, and (NiO) that additional mass percent is 0.6～1.2%
1-x(NbO
2.5)
x, wherein x=0.6～0.8; 0.2～0.5% (MnO)
1-y(NbO
2.5)
y, wherein y=0.4～0.6 and 3.0～4.0% CaZrO
3;
Described (NiO)
1-x(NbO
2.5)
xcompound is by NiO and Nb
2o
51-x:x/2 in molar ratio, wherein x=0.6～0.8 is synthetic;
Described (MnO)
1-y(NbO
2.5)
ycompound is by MnCO
3, Nb
2o
51-y:y/2 in molar ratio, wherein y=0.4～0.6 is synthetic;
Described CaZrO
3by CaCO
3and ZrO
21: 1 in molar ratio synthetic;
The preparation method of this unleaded high-k medium material for multilayer ceramic capacitors, has following steps:
(1) synthetic (NiO)
1-x(NbO
2.5)
xcompound, wherein x=0.6～0.8
By NiO, Nb
2o
51-x:x/2 in molar ratio, wherein x=0.6～0.8 batching, ball milling 4 hours after raw material mixes with deionized water, in 120 DEG C of oven dry, mistake 40 order sub-sieves, in 1000 DEG C of calcinings, is incubated 2 hours; Secondary ball milling 6 hours again, dries, crosses 80 order sub-sieves, makes (NiO)
1-x(NbO
2.5)
xcompound, wherein x=0.6～0.8;
(2) synthetic (MnO)
1-y(NbO
2.5)
ycompound, wherein y=0.4～0.6
By MnCO
3, Nb
2o
51-y:y/2 in molar ratio, wherein y=0.4～0.6 batching, ball milling 4 hours after raw material mixes with deionized water, in 120 DEG C of oven dry, mistake 40 order sub-sieves, in 800～1000 DEG C of calcinings; Secondary ball milling 6 hours again, dries, crosses 80 order sub-sieves, makes (MnO)
1-y(NbO
2.5)
ycompound, wherein y=0.4～0.6;
(3) synthetic CaZrO
3
By CaCO
3, ZrO
21:1 batching in molar ratio, ball milling 4 hours after raw material mixes with deionized water, in 120 DEG C of oven dry, mistake 40 order sub-sieves, in 1000 DEG C of calcinings, is incubated 2 hours, makes CaZrO
3;
(4) with BaTiO
3as base-material, the composition of additional following mass percent: 0.6～1.2% (NiO)
1-x(NbO
2.5)
x, wherein x=0.6～0.8; 0.2～0.5% (MnO)
1-y(NbO
2.5)
y, wherein y=0.4～0.6 and 3.0～4.0% CaZrO
3, institute joins raw material and mixes rear ball milling with deionized water 4～8 hours; The binding agent that after drying, additional mass percent is 7%, crosses 80 order sub-sieve granulations;
(5) the granulation powder of step (4) is pressed into green compact, after binder removal, in 1250 DEG C of sintering, is incubated 3 hours, make unleaded high-k medium material for multilayer ceramic capacitors.
2. unleaded high-k medium material for multilayer ceramic capacitors according to claim 1, is characterized in that, the CaZrO of described step (4)
3the mass percent of addition is 3.5%.
3. unleaded high-k medium material for multilayer ceramic capacitors according to claim 1, is characterized in that, the green compact of described step (5) are the disk green compact of Ф 15 × 1～1.3mm.
4. unleaded high-k medium material for multilayer ceramic capacitors according to claim 1, is characterized in that, the green compact of described step (5) were warming up to 550 DEG C of binder removals through 3.5 hours, then rose to 1250 DEG C of sintering through 1 hour, was incubated 3 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106938928A (en) * | 2017-03-31 | 2017-07-11 | 天津大学 | A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material |
| CN107188562A (en) * | 2017-06-23 | 2017-09-22 | 汕头市瑞升电子有限公司 | Stable ceramic capacitor dielectric of a kind of high-k low loss and high temperature and preparation method thereof |
| CN107399970A (en) * | 2017-07-13 | 2017-11-28 | 天津大学 | A kind of medium material for multilayer ceramic capacitors with superior insulation characteristics |
| JP7438944B2 (en) | 2017-12-01 | 2024-02-27 | レフラテクニック ホルディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Synthesis method for producing calcium zirconate-containing materials, as well as batch and crude ceramic refractory products with presynthesized calcium zirconate-containing particles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004284897A (en) * | 2003-03-24 | 2004-10-14 | Taiyo Yuden Co Ltd | Method of producing ceramic powder with perovskite structure, ceramic powder with perovskite structure, ceramic electronic component and its production method, and multilayer ceramic capacitor and its production method |
| CN101226827A (en) * | 2007-12-28 | 2008-07-23 | 天津大学 | Ultra-high dielectric constant multilayer ceramic capacitor medium and preparation method thereof |
| CN102807366A (en) * | 2012-08-08 | 2012-12-05 | 天津大学 | Multilayer ceramic capacitor dielectric with supper-wide work temperature range and preparation method thereof |
| CN103601486A (en) * | 2013-11-14 | 2014-02-26 | 天津大学 | Medium-temperature sintered multiplayer ceramic capacitor dielectric material and preparation method thereof |
-
2014
- 2014-06-24 CN CN201410288995.6A patent/CN104045341A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004284897A (en) * | 2003-03-24 | 2004-10-14 | Taiyo Yuden Co Ltd | Method of producing ceramic powder with perovskite structure, ceramic powder with perovskite structure, ceramic electronic component and its production method, and multilayer ceramic capacitor and its production method |
| CN101226827A (en) * | 2007-12-28 | 2008-07-23 | 天津大学 | Ultra-high dielectric constant multilayer ceramic capacitor medium and preparation method thereof |
| CN102807366A (en) * | 2012-08-08 | 2012-12-05 | 天津大学 | Multilayer ceramic capacitor dielectric with supper-wide work temperature range and preparation method thereof |
| CN103601486A (en) * | 2013-11-14 | 2014-02-26 | 天津大学 | Medium-temperature sintered multiplayer ceramic capacitor dielectric material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106938928A (en) * | 2017-03-31 | 2017-07-11 | 天津大学 | A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material |
| CN107188562A (en) * | 2017-06-23 | 2017-09-22 | 汕头市瑞升电子有限公司 | Stable ceramic capacitor dielectric of a kind of high-k low loss and high temperature and preparation method thereof |
| CN107399970A (en) * | 2017-07-13 | 2017-11-28 | 天津大学 | A kind of medium material for multilayer ceramic capacitors with superior insulation characteristics |
| JP7438944B2 (en) | 2017-12-01 | 2024-02-27 | レフラテクニック ホルディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Synthesis method for producing calcium zirconate-containing materials, as well as batch and crude ceramic refractory products with presynthesized calcium zirconate-containing particles |
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Application publication date: 20140917 |